JPH08231623A - New catalyst for olefin polymerization - Google Patents

Abstract

PURPOSE: To obtain a polymer having a narrow molecular weight distribution and being excellent in impact strength, stress cracking resistance, etc., at good efficiency by polymerizing an olefin in the presence of a specified catalyst comprising a transition metal compound. CONSTITUTION: An olefin (e.g. ethylene) is polymerized in the presence of a catalyst comprising a transition metal compound represented by formula I (Cp is a group having a cyclo-pentadienyl skeleton; M is Ti, Zr or Hf; L<1> is a a compound of formula, II; R<1> , R<2> , R<3> , R<4> , R<5> and R<6> are each H, halogen, (substituted) hydrocarbyl, alkoxy, thioalkoxy, aryloxy, thioaryloxy, amino or phosphino; and n is 1 or 2) [e.g. (pentamethylcyclopentadienyl)bis(8-quinolinolate) chlorozirconium].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel olefin polymerization catalyst and a method for olefin polymerization using the catalyst. More specifically, it is a transition metal compound having at least two kinds of ligands, and the transition metal is T
i, Zr, and Hf, one ligand is selected from a group having a cyclopentadienyl skeleton, and the other ligand is coordinated with an element selected from O, S, Se, and Te and an N element. The present invention relates to an olefin polymerization catalyst, which is selected from monovalent bidentate chelate anionic ligands, and a method for efficiently producing an olefin homopolymer or copolymer using this catalyst.

[0002]

2. Description of the Related Art In recent years, as a coordination polymerization catalyst for olefins, a polymerization method using a transition metal complex as a soluble polymerization catalyst component has been proposed. Representative examples of these transition metal complexes are roughly classified into two groups. One group is
It is a group of transition metal of Group 4A of the Periodic Table having two molecules of a ligand having a cyclopentadienyl skeleton, which is a group called a metallocene compound. For the method of using the metallocene compound as the olefin polymerization catalyst component, for example,
JP-A-58-19309 (EP069951),
JP-A-60-35007 (EP129368),
JP 61-130314 A (EP018591)
8), JP-A-1-301706 (EP14214)
3), JP-A-2-41303 (EP35139)
2) etc. The other group is a complex in which a molecule having a cyclopentadienyl skeleton and a donor molecule such as an amide are bridged to form a transition metal-containing condensed ring by coordination with a transition metal of Group 4A of the periodic table. , A group called a geometrically constrained compound. For the method of using the geometrically constrained compound as the olefin polymerization catalyst component, for example,
JP-A-3-163088 (EP416815),
Japanese Unexamined Patent Publication No. 5-194641 (EP502732),
JP-A-5-230123 (EP514828),
It is described in JP-A-6-306121. By using these transition metal complexes as the olefin polymerization catalyst component and using the aluminoxane or the cation generator as the co-catalyst component, the molecular weight distribution of the resulting polymer is narrow, and when the copolymerization reaction is performed, the copolymerizability is high. It is known that a copolymer having a uniform composition distribution can be obtained.

On the other hand, a method of using a transition metal complex of Group 4A of the Periodic Table, which is not included in these two groups, as an olefin polymerization catalyst component has been attempted, but the polymerization activity is lower than that of the above-mentioned two groups of transition metal complexes and is practical. Not reach the active area.
Among them, JP-A-5-170820 discloses a periodic table group 4A having one molecule of a ligand having a cyclopentadienyl skeleton and a chelate group having two oxygen atoms as coordination atoms. Transition metal complex CpM (R ¹ COCR ² CO
A method of using R ³ ) ₂ X as an olefin polymerization catalyst component is described. Also, Journal of Chemical Society, Chemical Communications (J. Chem. So
c., Chem. Commun., 18, 1415-1417 (1993)) has one molecule of a ligand having a cyclopentadienyl skeleton and a chelate group having two nitrogen atoms as coordination elements. Periodic Table 4 Group A Transition Metal Complex CpM ((NSiMe ₃ ) ₂ CP
h) A method of using X ₂ as an olefin polymerization catalyst component is described. However, these complex catalyst components also tend to have low activity.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a new type of transition metal complex which has not been known so far and has activity as an olefin polymerization catalyst component. O,
It is a feature that it is a transition metal complex having a specific monovalent bidentate chelate anionic ligand in which an element selected from S, Se and Te and an N element are coordinate atoms. By using the transition metal complex of the present invention as the olefin polymerization catalyst component, it is possible to produce a polymer in which the homopolymer or copolymer has a narrow molecular weight distribution and the copolymer has a uniform composition distribution.
Derived from these catalytic performances, the resulting polymer exhibits excellent physical properties in terms of impact strength, stress cracking resistance, transparency, low temperature heat sealability, blocking resistance, low stickiness, low extract, etc. be able to.

[0005]

In the olefin polymerization catalyst of the present invention, the transition metal is selected from Ti, Zr, and Hf, one ligand is selected from a group having a cyclopentadienyl skeleton, and the other is selected. The ligand is selected from a specific monovalent bidentate chelate anionic ligand in which an element selected from O, S, Se and Te and an N element are coordinate atoms, and the following general formula [1]
It is a transition metal compound having at least two kinds of ligands represented by

CpML ¹ _n Y _3-n ... [1] (In the formula [1], Cp is a group having a cyclopentadienyl skeleton, and M is Ti, Zr or Hf. L ¹ is L ^1. It is represented by the following general formula [2].

[0007]

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In the formula [2], R ¹ , R ² , R ³ , R ⁴ and R
⁵ , R ⁶ is a hydrogen atom, a halogen atom, an optionally substituted hydrocarbyl group, an alkoxy group or a hydrocarbylsilyl group. Alternatively, when two adjacent carbon atoms among the carbon atoms forming the skeleton have a hydrocarbyl group which may have a substituent, they may be bonded to each other to form a 4-, 5- or 6-membered ring. It is a base. X ¹ is O, S, Se or Te. Y is a halogen atom, a hydrocarbyl group which may have a substituent,
Alkoxy group, thioalkoxy group, aryloxy group,
It is a thioaryloxy group, an amino group or a phosphino group. n is 1 or 2. The olefin polymerization catalyst of the present invention is characterized by using these transition metal compounds and an organoaluminum oxy compound as a cocatalyst.

Further, the olefin polymerization catalyst of the present invention is
It is characterized in that these transition metal compounds are used in combination with a cation generator as a cocatalyst. Hereinafter, the present invention will be described in detail. In the present invention, the term "polymerization" is used to include not only homopolymerization but also copolymerization, and the term "polymer" includes not only homopolymer but also copolymer. Used as a meaning. Further, in the present invention, the term “hydrocarbyl” means alkyl, cycloalkyl, alkenyl, arylalkyl,
Aryl and alkylaryl are used as a meaning that includes.

The transition metal compound of the present invention is a compound having a composition represented by the following general formula [1]. CpML ¹ _n Y _3-n ... [1] In the formula [1], M means a central metal, and is a transition metal which is Zr, Ti or Hf.

The ligand Cp is a group having a cyclopentadienyl skeleton, and is a cyclopentadienyl group, a substituted cyclopentadienyl group, or two adjacent carbon atoms of the cyclopentadienyl ring are other carbon atoms. It means a cyclopentadienyl group which is bonded to an atom to form a 4-, 5- or 6-membered ring. The substituted cyclopentadienyl group has 1 to 5
With a range of substituents. The substituent is a hydrocarbyl group having 1 to 20 carbon atoms or a hydrocarbylsilyl group having 1 to 20 carbon atoms. The cyclopentadienyl group in which two carbon atoms of the cyclopentadienyl ring are bonded to another carbon atom to form a 4-, 5- or 6-membered ring includes an indenyl group, a tetrahydroindenyl group,
Fluorenyl group and the like. These groups may have a substituent such as a hydrocarbyl group having 1 to 20 carbon atoms or a hydrocarbylsilyl group having 1 to 20 carbon atoms.

Examples of the group having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group and iso.
-Propylcyclopentadienyl group, n-butylcyclopentadienyl group, iso-butylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,
3-dimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group ,
Trimethylsilylcyclopentadienyl group, trimethylsilyltetramethylcyclopentadienyl group, (phenyldimethylsilyl) cyclopentadienyl group, triphenylsilylcyclopentadienyl group, 1,3-di (trimethylsilyl) cyclopentadienyl group, Cyclohexylcyclopentadienyl group, allylcyclopentadienyl group, benzylcyclopentadienyl group, phenylcyclopentadienyl group, tolylcyclopentadienyl group,
Indenyl group, 1-methylindenyl group, 2-methylindenyl group, 4-methylindenyl group, 5-methylindenyl group, 2,4-dimethylindenyl group, 4,7-dimethylindenyl group, 2 -Methyl-4-ethyl-indenyl group, 2-methyl-4,6-diiso-propyl-indenyl group, naphthylindenyl group, 4,5,6,7-
Examples thereof include a tetrahydroindenyl group, a 2-methyltetrahydroindenyl group, a fluorenyl group, a 2-methylfluorenyl group, and a 2,7-ditert-butylfluorenyl group.

The bidentate chelating ligand L ¹ is represented by the following general formula [2].

[0014]

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In the formula [2], R¹, R², R³, R^Four, R
^Five, R⁶Has a hydrogen atom, a halogen atom, and a substituent
Optionally hydrocarbyl group, alkoxy group, hydrocarbyl group
Bilsilyl group. Or of the carbon atoms forming the skeleton
Two adjacent carbon atoms may have a substituent
If they have different hydrocarbyl groups,
Is a group which may form a 4-, 5- or 6-membered ring. An example
For example, hydrogen atom, fluorine, chlorine, bromine and iodine halogen
Group atom, methyl group, ethyl group, n-propyl group, iso
-Various structural isomers such as propyl group and tert-butyl group
C1-C20 alkyl group having a cyclopentyl group
And cycloalkyl having 5 to 20 carbon atoms such as cyclohexyl group
Group, phenyl group, tolyl group, methoxyphenyl group and
Aryl group having 6 to 20 carbon atoms such as futyl group, benzyl group
Arylalkyl having 7 to 20 carbon atoms such as and neophyll groups
Group, allyl group, 2-butenyl group and the like having 2 to 20 carbon atoms.
Lucenyl group, methoxy group, ethoxy group, phenoxy group, etc.
An alkoxy group having 1 to 20 carbon atoms, a carbon atom having 1 to 20 carbon atoms
And a doloalkylsilyl group. These groups are hydrogen
The child may be substituted with a halogen atom. Carbocycle shape
As an example of the formed skeletal structure, R^FourAnd R^FiveCombined with fragrance
Quinoline structure forming a 6-membered ring, R¹And R ², R^FourWhen
R^FiveEach of which is bonded to form an aromatic 6-membered ring.
Lysine structure, R²And R³Or R³And R^FourJoined together
Examples include an isoquinoline structure that forms an aromatic 6-membered ring.
It

X ¹ is O, S, Se or Te. Y in the formula [1] is a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms and optionally having a substituent, and 1 to 2 carbon atoms.
0 alkoxy group, C1-20 thioalkoxy group, C6-20 aryloxy group, C6-2
A thioaryloxy group having 0, an amino group having 1 to 20 carbon atoms, or a phosphino group having 1 to 20 carbon atoms. For example,
Halogen atoms such as fluorine, chlorine, bromine and iodine, methyl group, ethyl group, n-propyl group, iso-propyl group and t
1 to 6 carbon atoms having various structural isomer groups such as ert-butyl group
20 alkyl group, cycloalkyl group having 5 to 20 carbon atoms such as cyclopentyl group and cyclohexyl group, aryl group having 6 to 20 carbon atoms such as phenyl group, tolyl group and methoxyphenyl group, carbon such as benzyl group and neophyll group Number 7 ~
20 arylalkyl group, alkenyl group having 2 to 20 carbon atoms such as allyl group and 2-butenyl group, alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group and n-butoxy group, thioisopropoxy group and A thioalkoxy group substituted with a hydrocarbon group having 1 to 20 carbon atoms such as a thiobenzylalkoxy group, an aryloxy group having 6 to 20 carbon atoms such as a phenoxy group or a p-tolyloxy group, and a carbon number 6 such as a thiophenoxy group. To 20 thioaryloxy group, di-n-propylamino group, dibenzylamino group and the like having 1 to 20 carbon atoms
1-20 carbon atoms such as amino group, diisoamylphosphino group and diphenylphosphino group substituted by the hydrocarbon group of
And a phosphino group substituted by the hydrocarbon group of.

In the formula [1], n is 1 or 2. Specific examples of the transition metal compound represented by the above general formula [1] include the following compounds. However,
It is not limited by these examples. (Cyclopentadienyl) bis (2-pyridinemethanolate) chlorozirconium, (n-butylcyclopentadienyl) bis (2-pyridinemethanolate) chlorozirconium, (1,3-dimethylcyclopentadienyl) bis ( 2-pyridinemethanolate) chlorozirconium,
(Pentamethylcyclopentadienyl) bis (2-pyridinemethanolate) chlorozirconium, (indenyl) bis (2-pyridinemethanolate) chlorozirconium, (cyclopentadienyl) bis (3-ethoxy-
2-Pyridine methanolate) bromozirconium, (cyclopentadienyl) bis (2-pyridinemethylthiolate) chlorozirconium, (methylcyclopentadienyl) bis (2-pyridinemethanolate) chlorozirconium, (methylcyclopentadienyl) ) Bis (4-methyl-2-pyridinemethanolate) chlorozirconium, (n-propylcyclopentadienyl) bis (3,3)
4-dimethyl-2-pyridinemethanolate) methylzirconium, (n-butylcyclopentadienyl) bis (2-pyridine-phenylmethanolate) chlorozirconium, (n-butylcyclopentadienyl) bis (2
-Pyridine methanolate) ethoxy zirconium, (n
-Butylcyclopentadienyl) bis (2-pyridinemethylthiolate) phenylzirconium, (1,3-dimethylcyclopentadienyl) bis (3-propyl-2)
-Pyridine methanolate) chlorozirconium, (1,
2,4-trimethylcyclopentadienyl) bis (3-
Propyl-2-pyridine-1-ethanolate) benzylzirconium, (tetramethylcyclopentadienyl)
Bis (4-chloro-2-pyridinemethanolate) chlorozirconium, (pentamethylcyclopentadienyl)
Bis (2-pyridinemethanolate) chlorozirconium, (pentamethylcyclopentadienyl) bis (2-
(Pyridine-diphenyl-methanolate) chlorozirconium, (trimethylsilylcyclopentadienyl) bis (2-pyridine-2-methyl-1-propanolate) chlorozirconium, (trimethylsilyltetramethylcyclopentadienyl) bis (2-pyridinemethanolate) Chlorozirconium, (indenyl) bis (2-pyridinemethanolate) phenoxyzirconium, (indenyl) bis (2-pyridinemethylthiolate) chlorozirconium, (tetrahydroindenyl) bis (4-
Methyl-2-pyridinemethanolate) dimethylaminozirconium, (2,4,6-trimethylindenyl) bis (2-pyridinemethanolate) diphenylphosphinozirconium, (fluorenyl) bis (2-pyridine-
Phenyl-methanolate) chlorozirconium, (2,
7-ditertbutylfluorenyl) bis (2-pyridinemethanolate) chlorozirconium, (cyclopentadienyl) (2-pyridinemethanolate) dichlorozirconium, (cyclopentadienyl) (2-pyridinemethylthiolate) dichloro Zirconium, (methylcyclopentadienyl) (2-pyridinemethanolate) chlorozirconium, (n-propylcyclopentadienyl) (3,4-dimethyl-2-pyridinemethanolate)
Dimethylzirconium, (n-butylcyclopentadienyl) bis (2-pyridine-phenylmethanolate) dichlorozirconium, (1,3-dimethylcyclopentadienyl) (3-propyl-2-pyridinemethanolate) diethoxyzirconium , (1,2,4-trimethylcyclopentadienyl) (3-propyl-2-pyridine-1-ethylthiolate) dibenzylzirconium,
(Tetramethylcyclopentadienyl) (4-chloro-
2-pyridine methanolate) diallyl zirconium,
(Pentamethylcyclopentadienyl) bis (2-pyridinemethanolate) diiodozirconium, (trimethylsilyltetramethylcyclopentadienyl) (2-pyridinemethanolate) methylphenylzirconium,
(Indenyl) (2-pyridinemethanolate) diaminozirconium, (tetrahydroindenyl) (3-ethoxy-2-pyridinemethanolate) didiphenylphosphinozirconium, (fluorenyl) (2-pyridine-
(Methanolate) dichlorozirconium, (cyclopentadienyl) bis (8-quinolinolate) chlorozirconium, (n-butylcyclopentadienyl) bis (8-
(Quinolinolate) chlorozirconium, (1,3-dimethylcyclopentadienyl) bis (8-quinolinolate) chlorozirconium, (pentamethylcyclopentadienyl) bis (8-quinolinolate) chlorozirconium, (indenyl) bis (8-quinolinolate ) Chlorozirconium, (cyclopentadienyl) bis (8-
(Quinolinolate) bromozirconium, (cyclopentadienyl) bis (5-chloro-8-quinolinolate) chlorozirconium, (methylcyclopentadienyl) bis (5-chloro-7-iodo-8-quinolinolate) i
So-propylzirconium, (methylcyclopentadienyl) bis (2-methyl-8-quinolinolate) chlorozirconium, (ethylcyclopentadienyl) bis (10-acridinolate) chlorozirconium, (ethylcyclopentadienyl) Bis (2,7-dimethyl-
8-quinolinolate) phenyl zirconium, (n-propylcyclopentadienyl) bis (2-ethyl-5-
Iodo-8-quinolinolate) chlorozirconium,
(N-Butylcyclopentadienyl) bis (10-acridinolate) chlorozirconium, (1,3-dimethylcyclopentadienyl) bis (8-quinolinolate)
Cyclohexyl zirconium, (1,3-dimethylcyclopentadienyl) bis (7-n-propyl-8-quinolinolate) chlorozirconium, (1,2,4-trimethylcyclopentadienyl) bis (7-chloro-8-
(Quinolinolate) chlorozirconium, (tetramethylcyclopentadienyl) bis (8-quinolinolate) benzylzirconium, (pentamethylcyclopentadienyl) bis (2-methyl-8-quinolinolate) chlorozirconium, (trimethylsilyltetramethylcyclopentadiene) (Enyl) bis (8-quinolinolate) chlorozirconium, (indenyl) bis (8-quinolinolate) chlorozirconium, (fluorenyl) bis (7-
Chloro-8-quinolinolate) chlorozirconium,
(Cyclopentadienyl) (8-quinolinoleate) dichlorozirconium, (methylcyclopentadienyl)
(10-acridinolate) diphenoxyzirconium, (ethylcyclopentadienyl) (7-chloro-8
-Quinolinolate) dibromozirconium, (n-propylcyclopentadienyl) (8-quinolinolate) dicyclohexylzirconium, (n-butylcyclopentadienyl) bis (8-quinolinolate) diaminozirconium, (1,3-dimethylcyclopentadienyl) Enil)
(10-acridinolate) dichlorozirconium,
(1,2,4-trimethylcyclopentadienyl) (8
-Quinolinolate) dichlorozirconium, (pentamethylcyclopentadienyl) (2-methyl-8-quinolinolate) dimethoxyzirconium, (indenyl)
(8-quinolinolate) dichlorozirconium, (fluorenyl) (7-n-propyl-8-quinolinolate)
Examples thereof include compounds such as dichlorozirconium.

Further, in the zirconium compound as in the above example, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can be mentioned as a specific example. Transition metal compound CpML ¹ _n
Y _3-n can be produced by several methods. For example,
This is a method of producing from a Group 4A transition metal compound [3] and a compound represented by the following general formula [4] according to the following reaction formula [5].

CpMY ₃ ... [3] In the formula [3], M, Cp and Y have the same meanings as in the general formula [1]. L ¹ H ... [4] In the formula [4], L ¹ has the same meaning as in the general formula [1] and is represented by the general formula [2].

CpMY ₃ + L ¹ H → CpML ¹ _n Y _3-n + HY ... [5] In this reaction, compound [4] is equivalent to compound [3] in the case of n = 1, When n = 2, it is efficient to use a double molar amount. Further, the transition metal compound CpML ¹ ₂ Y with n = 2 can be efficiently produced from the metallocene compound represented by the following general formula [6] and the compound [4] according to the following reaction formula [7]. Can be mentioned.

Cp ₂ MY ₂ ... [6] In the formula [6], M, Cp and Y have the same meanings as in the general formula [1]. Cp ₂ MY ₂ + 2L ¹ H → CpML ¹ ₂ Y + CpH + HY ... [7] As an example of this reaction, (cyclopentadienyl) bis (8
-Quinolinolate) fluorotitanium, (cyclopentadienyl) bis (8-quinolinolate) chlorotitanium, (cyclopentadienyl) bis (8-quinolinolate) bromotitanium, (cyclopentadienyl) bis (8-quinolinolate) chlorozirconium , (Cyclopentadienyl) bis (8-quinolinolate) bromozirconium, (Cyclopentadienyl) bis (8-quinolinolate) chlorohafnium Journal Chemical Society (A) (J. Chem. Soc. (A)), 15 , 2487-2
491 (1971), other related compounds can be synthesized by the same method.

In any of the reactions of the reaction formulas [5] and [7], the objective product can be efficiently produced by adding a tertiary amine such as triethylamine or triisobutylamine for the purpose of trapping HY by-produced. it can. In this case, the added tertiary amine is the compound [4],
It is usually used in an amount in the range of 1 to 100 times. In either case of the reaction formulas [5] and [7], the reaction conditions include a reaction temperature of -20 ° C to 100 ° C, preferably 0 ° C to 80 ° C, and a reaction time of 0.1 to 50 hours. Preferably 0.
It is in the range of 5 to 30 hours. Solvents used in the reaction include aliphatic hydrocarbons such as hexane and decane, ethers such as diethyl ether and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene and xylene, halogens such as carbon tetrachloride, chloroform and methylene chloride. Used are hydrocarbon compounds, nitrogen compounds such as acetonitrile and pyridine, and the like. Of these, acetonitrile is preferred. Such a reaction solvent is generally used in an amount within the range of 10 to 500 times the amount of the compound [3] or [6].

The desired transition metal compound can be produced by the above-mentioned production method and the like. The transition metal compound thus produced can be purified by isolating the filtrate obtained by filtering the reaction solution under reduced pressure, recrystallizing and drying under reduced pressure. The cocatalyst which can make these transition metal compounds effective as a catalyst for olefin polymerization according to the present invention is an organoaluminum oxy compound and / or a cation generator, and compounds conventionally known in the art can be used. .

That is, the organoaluminum oxy compound is an alkylaluminoxane represented by the following general formulas [8] and [9].

[0025]

[Chemical 4]

[0026]

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In the formulas [8] and [9], R ⁷ is a hydrogen atom,
A halogen atom or an alkyl group having 1 to 10 carbon atoms,
p is an integer of 2-40. As an example of R ^7, a hydrogen atom,
Halogen atom such as chlorine and bromine, methyl group, ethyl group and n
-Propyl group, iso-propyl group, n-butyl group, i
Examples thereof include alkyl groups such as so-butyl group, sec-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group, and mixtures thereof, but especially methyl group or methyl group and others Mixtures of groups of are preferred. The repeating number p is preferably selected from the range of 2 to 40, and more preferably 5 or more.
A known method for synthesizing this alkylaluminoxane, for example, a method in which a trialkylaluminum is dissolved in a hydrocarbon solvent, and water is gradually added in an amount equivalent to the trialkylaluminum in this solution to hydrolyze it, a hydrocarbon solvent is used. Copper sulfate hydrate or aluminum sulfate hydrate is suspended, and 1 to 3 equivalents of trialkylaluminum is brought into contact with the hydrated water of crystallization in this suspension, and trialkylaluminum is slowly hydrolyzed. It can be produced by a method of decomposing, or a method of slowly hydrolyzing trialkylaluminum by contacting 1 to 3 times equivalent amount of trialkylaluminum with adsorbed water of undehydrated silica gel suspended in a hydrocarbon solvent. .

On the other hand, examples of the cation generator include neutral type and ion pair type, and examples of the neutral type include organic boron compounds represented by the following general formula [10]. BR ⁸ ₃ ... [10] In the formula [10], R ⁸ is a hydrocarbyl group having 1 to 20 carbon atoms. That is, the boron compound is not particularly limited as long as it is a boron compound in which a hydrocarbyl group is bonded to boron as a substituent, and any compound can be used. In these groups, a hydrogen atom may be replaced with a halogen atom.

Examples of R ⁸ include methyl group, ethyl group and n-
Examples thereof include an alkyl group such as a propyl group, an amyl group, an iso-amyl group, an iso-butyl group, and an n-octyl group, or an aryl group such as a phenyl group, a fluorophenyl group, a tolyl group, and a xylyl group. The three R ⁸ may be the same as or different from each other. This general formula [11]
Specific examples of the organoboron compound represented by: triphenylboron, tri (pentafluorophenyl) boron, tri (2,3,4,5-tetrafluorophenyl)
Boron, tri (2,4,6-trifluorophenyl) boron, tri (2,3-difluorophenyl) boron, tri (2-fluorophenyl) boron, tri [(3,5-
Di (trifluoromethyl) phenyl] boron, tri [(4- (trifluoromethyl) phenyl] boron, trimethylboron, triethylboron, tri (trifluoromethyl) boron, diphenylfluoroboron, di (pentafluorophenyl) chloroboron, etc. Among these, tri (pentafluorophenyl) boron is particularly desirable.

The ion pair type cation generator is a cation generator represented by the following general formula [11]. [On] + [BR ⁹ ₄ ] −... [11] In the formula [11], [On] + is a metal cation such as 1B group, 2B group, or 8 group metal ion, or carbonium or silonium. , Oxonium, sulfonium, ammonium, and onium such as phosphonium,
[BR ⁹ ₄ ] -is an anion having a non-coordinating property or a poor coordinating property. R ⁹ is the same as R ⁸ in the general formula [10]. Examples of preferable general formula [11] are ferrocenium tetra (pentafluorophenyl) borate, silver (I) tetra (pentafluorophenyl) borate, copper (I) tetra (pentafluorophenyl) borate, and mercury (II).
Bis (tetra (pentafluorophenyl) borate, palladium (II) bis (tetra (pentafluorophenyl) borate, platinum (II) bis (tetra (pentafluorophenyl) borate, diphenylhydrocarbonium tetra (pentafluorophenyl) borate, Triphenyl carbonium tetra (pentafluorophenyl)
Borate, triphenylsilonium tetra (pentafluorophenyl) borate, tricyclohexylcarbonium tetra (pentafluorophenyl) borate, triethyloxonium tetra (pentafluorophenyl)
Borate, triethylsulfonium tetra (pentafluorophenyl) borate, diethylanilinium tetra (pentafluorophenyl) borate, trimethylammonium tetra (pentafluorophenyl) borate, triethylammonium tetra (pentafluorophenyl) borate, tetra-n-butyl Examples thereof include tetra (pentafluorophenyl) borate salts such as ammonium tetra (pentafluorophenyl) borate and triphenylphosphonium tetra (pentafluorophenyl) borate.

The purpose of stabilizing the catalyst in the practice of the present invention,
For the purpose of stabilizing the co-catalyst organoaluminum oxy compound and / or the cation generator and reducing the amount used, an alkylaluminum represented by the general formula [12] can be coexisted as a co-catalyst. (R ¹⁰ ₃ Al) q ... [12] In the formula [13], R 10 represents a hydrogen atom, a halogen group, or an alkyl group having 1 to 10 carbon atoms, and q is 1 or 2. Examples of R ¹⁰ are hydrogen atom, halogen atom such as chlorine and bromine, methyl group, ethyl group, n-propyl group and iso-
Propyl group, n-butyl group, iso-butyl group, sec
Examples include -butyl group, pentyl group, hexyl group, octyl group, alkyl group such as decyl group, and a mixture thereof.

In the present invention, in carrying out the olefin polymerization, the catalyst component which is the transition metal compound of the present invention, the organoaluminum oxy compound which is the co-catalyst and / or the cation generator and the alkylaluminum are used as an inert hydrocarbon solvent. It can be prepared by adding and dissolving it in the medium or in the olefin medium used for the polymerization. The order of addition at this time is arbitrarily selected, and the transition metal compound of the present invention and the cocatalyst may be mixed and used in advance before the polymerization, or may be independently added and used in the polymerization reaction system.
In the present invention, in addition to the above-mentioned components, other components effective for olefin polymerization may be contained. Furthermore, when multimodal polymerization or the like is performed to improve polymer properties, the transition metal compounds of the present invention can be used in combination of two or more kinds, or can be used in combination with other catalyst components known in the art.

The transition metal compound of the present invention used for olefin polymerization is usually used at a catalyst concentration in the range of 10 ^-8 to 10 ^-1 mol / liter, preferably 10 ^-7 to 10 ^-3 mol / liter. On the other hand, when the organoaluminum oxy compound is used as the co-catalyst, the ratio of aluminum atom / transition metal atom is usually 1 with respect to the transition metal compound.
It is used in the range of 0 to 10 ⁵ , preferably 50 to ⁵ × 10 ³ . When the cation generator is used as a cocatalyst, the cation generator / transition metal compound molar ratio is usually 0.5 to 10, preferably 1 to 3 with respect to the transition metal compound. . Further, when the alkylaluminum is used, with respect to the transition metal compound,
Aluminum atom / transition metal atom ratio is usually 1 to 1
It is used in the range of 0 ⁵ , preferably 10 to 10 ⁴ .

When a transition metal compound having a bivalent monovalent bidentate chelate anionic ligand is used as a catalyst among the transition metal compounds according to the present invention, pretreatment before the polymerization improves the polymerization activity. May be desirable to do. It is particularly effective when the polymerization temperature is about 90 ° C. or lower. As the method of pretreatment, a method of mixing the transition metal compound, the cocatalyst, and the olefin in an inert hydrocarbon solvent and heating and holding the resulting mixed solution can be adopted.
The amount ratio of the transition metal compound to the cocatalyst may be within the range of the amount ratio relationship used in the polymerization reaction. The olefin may be the olefin itself used for the polymerization reaction or a carbon number of 2 to 20
Olefins within the range of 10 to 10 can be employed, and the amount of olefins is about 10 to 10 in terms of olefin / transition metal compound molar ratio.
It may be used within the range of 3. Conditions for heating and holding the mixed solution are a temperature of about 90 ° C to 120 ° C and a time of about 10 minutes to 6
You can choose from a time of 0 minutes.

In the present invention, the polymerization can be carried out by any of the polymerization methods such as slurry polymerization, solution polymerization and gas phase polymerization. When carrying out slurry polymerization or gas phase polymerization,
Either or both of the catalyst component which is the transition metal compound and the co-catalyst can be supported on a carrier for use. Examples of the carrier include inorganic oxide carriers such as silica, alumina, silica-alumina, magnesia, titania and zirconia, inorganic carriers such as magnesium chloride, organic carriers such as polystyrene, polyethylene, polypropylene and carbon. The method of loading on a carrier is not particularly limited, and a method known in the art can be used. The catalyst supported on the carrier may preliminarily polymerize olefin during olefin polymerization. In the prepolymerization, the olefin polymer is 0.05 to 500 per 1 g of the supported catalyst.
It is preferred to prepolymerize in an amount of g, preferably 0.1 to 100 g. The method of carrying a catalyst and / or a co-catalyst on a carrier for polymerization is effective in improving the particle shape and bulk density of the produced polymer in the case of slurry polymerization or gas phase polymerization.

When carrying out solution polymerization or slurry polymerization, an inert hydrocarbon solvent or the olefin itself used for the polymerization can be used as a solvent. Specific examples of the inert hydrocarbon solvent include butane, iso-butane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane. And alicyclic hydrocarbons, benzene, toluene, xylene, and other aromatic hydrocarbons, naphtha, kerosene, light oil, and other petroleum fractions.

In the present invention, when carrying out slurry polymerization, the polymerization temperature is usually in the range of -20 to 100 ° C, preferably 20 to 90 ° C. When carrying out the solution polymerization, the polymerization temperature is usually 0 to 300 ° C, preferably 100 to 250 ° C. When carrying out gas phase polymerization, the polymerization temperature is usually 0 to 1.
The temperature is preferably 20 ° C, preferably 20 to 100 ° C.

The polymerization pressure is not particularly limited, but is usually atmospheric pressure to 300 kg / cm 2, preferably atmospheric pressure to 100 kg /.
The condition of cm2 can be adopted. The polymerization can be carried out in any of batch system, anti-continuous system and continuous system. It is also possible to carry out the polymerization in two or more stages under different reaction conditions. The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization reaction system or by changing the polymerization temperature.

The olefins which can be polymerized by the olefin polymerization method of the present invention include ethylene and olefins having 3 to 20 carbon atoms, such as propylene.
1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-
Eicosene, cyclic olefins having 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5
-Methyl-2-norbornene, tetracyclododecene,
2-methyl-1,4,5,8-dimethano-1,2,3,
4,4a, 5,8,8a-octahydronaphthalene and the like can be mentioned. Further, styrene, vinylcyclohexene, diene and the like can also be used. Also, ethylene / propylene, ethylene / 1-butene, ethylene / 1
-Hexene, ethylene / 1-octene, ethylene / cyclopentene, ethylene / styrene, ethylene / propylene / ethylidene norbornene, etc. are copolymerized by combining two or more olefins and copolymerized with a uniform composition distribution and a low-density copolymer. Coalescence can be produced.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to these Examples. In synthesizing the transition metal compound of the present invention, 8-quinolinol as a raw material is a commercially available product or a literature (Zesz. Nauk. Politech. Rzeszowskiej, 3, 63 (1984)).
Etc.) or a method similar thereto was used. Pyridine methanol is a commercially available product or literature (Synthetic Communications, 25, 629 (1995), etc.)
What was synthesize | combined by the method as described in 1 or the method according to it was used. As the metallocene compound and the transition metal compound, commercially available products or compounds synthesized by a method known in the art were used.

All the synthesis and isolation of the catalyst were carried out in a Schlenk method or a glove box under a nitrogen atmosphere. The raw material compound and the produced transition metal compound were identified by elemental analysis and 1 H-NMR. The molecular weight and molecular weight distribution of the homopolymer or copolymer obtained by the polymerization reaction were measured from the differential refractive index using 150CV gel permeation chromatography (GPC) manufactured by Waters. The comonomer distribution of the copolymer obtained by the copolymerization reaction is M55 manufactured by Nicolet Co. linked to the GPC.
0 Fourier transform infrared spectrophotometer (FT-IR). Catalyst synthesis

[0042]

Example 1 (Pentamethylcyclopentadienyl) bis (8-quinolinolate) chlorozirconium {Cp ^* Zr (C ₉ H
Synthesis of ₆ NO) ₂ Cl} (Catalyst 1) In a glass reactor having an inner volume of 100 ml which was sufficiently replaced with nitrogen, 2.0 g of (pentamethylcyclopentadienyl) zirconium trichloride in acetonitrile solution 50
3.5 g of 8-quinolyl was added to ml, and the mixture was added at room temperature to 12
Stirred for hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to obtain 2.7 g of a yellow solid (yield 81%). 1H-NMR of product
(Δ: ppm, solvent: deuterated chloroform) and elemental analysis results (% by weight) are shown below.

Δ1.9 (s, 18H), 7.0 (m, 6)
H), 7.4 (m, 2H), 7.8 (d, 1H), 7.
9 (d, 1H), 8.1 (d, 1H), 8.5 (d, 1)
H), C: 61.4, H: 5.5, N: 4.8,
Zr: 16.4

[0044]

Example 2 (1,3-Dimethylcyclopentadienyl) bis (3-
Ethoxy-2-pyridine-1-ethanolate) chlorozirconium {(1,3-Me ₂ Cp) Zr (EtOC _{4
H 3 N-MeCHO) 2 Cl} } ( catalyst 2) synthesized in sufficiently purged with nitrogen content volume glass reactor of 100ml of bis (1,3-dimethyl cyclopentadienyl)
3.8 g of 3-ethoxy-2-pyridine-1-ethanol was added to 50 ml of an acetonitrile solution of 2.0 g of zirconium dichloride, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to obtain 2.2 g of a white solid (yield 68%). The results of elemental analysis (% by weight) are shown below.

C: 54.0, H: 6.2, N: 5.5,
Zr: 16.2

[0046]

Example 3 (Trimethylsilyltetramethylcyclopentadienyl) (4-methyl-2-pyridine-methanolate) dichlorozirconium {(Me ₃ SiMe ₄ Cp) Zr (O
Synthesis of CH _2-4 -MeC ₅ H ₃ N) Cl ₂ } (Catalyst 3) (Trimethylsilyltetramethylcyclopentadienyl) zirconium trichloride 2. 0.6 g of 4-methyl-2-pyridine-methanol and 0.5 g of triethylamine were added to 50 ml of a 0 g acetonitrile solution, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to obtain 1.5 g of a yellow solid (yield 63%). The results of elemental analysis (% by weight) are shown below.

C: 47.2, H: 6.6, N: 3.2,
Zr: 19.5

[0048]

Example 4 (Pentamethylcyclopentadienyl) bis (2-pyridine-methanolate) chlorotitanium {Cp ^* Ti
Synthesis of (OCH ₂ -C ₅ H ₄ N) ₂ Cl} (Catalyst 4) In a glass reactor with an internal volume of 100 ml which had been sufficiently replaced with nitrogen, 2.0 g of (pentamethylcyclopentadienyl) titanium trichloride was added. Acetonitrile solution 50m
2-Pyridine-methanol (1.5 g) and triethylamine (1.4 g) were added to 1 and stirred at room temperature for 12 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to obtain 1.2 g of a yellow oily substance (yield 41%). The results of elemental analysis (% by weight) are shown below.

C: 61.1, H: 6.0, N: 6.8,
Ti: 10.7

[0050]

Example 5 (Cyclopentadienyl) bis (7-n-propyl-8)
-Quinolinolate) chlorozirconium {CpZr (7
In _{-nP r-C 9 H 5 NO} ) 2 Cl} ( catalyst 5) Synthesis sufficiently purged with nitrogen glass reactor having an inner volume of 100ml of bis (acetonitrile cyclopentadienyl) zirconium dichloride 2.0g solution 8-to 50 ml
Quinoril (5.1 g) was added, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to give a yellow solid of 2.7.
g was obtained (yield 71%). The results of elemental analysis (% by weight) are shown below.

C: 61.0, H: 5.6, N: 4.6,
Zr: 16.5

[0052]

Example 6 (n- butylcyclopentadienyl) bis (5-chloro-7-iodo-8-quinolinolato) chloro zirconium {(nB uCp) Zr (5 -Cl-7-I-C 9 H 4
Synthesis of NO) ₂ Cl} (Catalyst 6) In a glass reactor having an inner volume of 100 ml which was sufficiently replaced with nitrogen, 2.0 g of bis (n-butylcyclopentadienyl) zirconium dichloride in acetonitrile solution 50
5-chloro-7-iodo-8-quinolinol 2.
1 g was added, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to obtain 2.8 g of a yellow solid (yield 67
%). The results of elemental analysis (% by weight) are shown below.

C: 37.3, H: 2.7, N: 3.5,
Zr: 10.5

[0054]

Example 7 (1,3-Dimethylcyclopentadienyl) bis (8-
Quinoline-thiolate) chlorozirconium {(1,3
Synthesis of —Me ₂ Cp) Zr (C ₉ H ₆ NS) ₂ Cl} (Catalyst 7) Bis (1,3-dimethylcyclopentadienyl) was prepared in a glass reactor having an inner volume of 100 ml which had been sufficiently replaced with nitrogen.
2.9 g of 8-quinolinethiol was added to 50 ml of an acetonitrile solution containing 2.0 g of zirconium dichloride,
Stir at room temperature for 18 hours. After drying the reaction solution under reduced pressure,
Toluene was added and filtered. The filtrate was concentrated and pentane was added to obtain 1.3 g of a yellow solid (yield 54%). The results of elemental analysis (% by weight) are shown below.

C: 56.3, H: 3.6, N: 5.5,
S: 11.5, Zr: 16.9

[0056]

Example 8 (Cyclopentadienyl) bis (8-quinolinolate)
Chlorohafnium {CpHf (C ₉ H ₆ NO) ₂ Cl}
Synthesis of (Catalyst 8) In a glass reactor having an inner volume of 100 ml which had been sufficiently replaced with nitrogen, 3.1 g of 8-quinolinol was added to 50 ml of an acetonitrile solution containing 2.0 g of bis (cyclopentadienyl) hafnium dichloride, and the mixture was cooled to room temperature It was stirred at 18 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to bring the yellow solid to 1.0.
g was obtained (yield 32%). The results of elemental analysis (% by weight) are shown below.

C: 48.4, H: 3.0, N: 4.7,
Hf: 31.2

[0058]

Example 9 (n-Butylcyclopentadienyl) bis (2-pyridine-phenylmethanolate) chlorozirconium {(n
B uCp) Zr (OCPhH-C 5 H 4 N) 2 Cl}
Synthesis of (Catalyst 9) 2 g of an acetonitrile solution containing 2.0 g of bis (n-butylcyclopentadienyl) zirconium dichloride was prepared in a glass reactor having an inner volume of 100 ml which had been sufficiently replaced with nitrogen.
-Pyridine-phenylmethanol (1.8 g) and triethylamine (0.5 g) were added, and the mixture was stirred at room temperature for 18 hours.
The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to obtain 2.1 g of a white solid (yield 70%). The results of elemental analysis (% by weight) are shown below.

C: 64.0, H: 5.2, N: 4.6,
Zr: 15.0

[0060]

Example 10 (Indenyl) bis (2-pyridine-methylthiolate) chlorozirconium {(Ind) Zr (SCH ₂ —
Synthesis of C ₅ H ₄ N) ₂ Cl} (Catalyst 10) 2-pyridine-methylthiol was added to a solution of 2.0 g of bis (indenyl) zirconium dichloride in acetonitrile in a glass reactor having an inner volume of 100 ml which was sufficiently replaced with nitrogen. 1.1 g and triethylamine 0.5g were added and it stirred at room temperature for 18 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to obtain 1.4 g of a yellow solid (yield 65%). The results of elemental analysis (% by weight) are shown below.

C: 51.1, H: 4.2, N: 5.7,
S: 12.9, Zr: 18.6

[0062]

Example 11 (1,2,4-Trimethylcyclopentadienyl) bis (2-pyridine-iso-propyl-methanolate) phenylzirconium {(1,2,4-Me ₃ Cp) Zr
Synthesis of (OCHiP r-C ₅ H ₄ N) ₂ Ph} (Catalyst 11) Bis (1,2,4-trimethylcyclopentadienyl) zirconium was prepared in a glass reactor with an internal volume of 100 ml which had been sufficiently replaced with nitrogen. 3.2 g of 2-pyridine-iso-propylmethanol was added to an acetonitrile solution of 2.0 g of dichloride, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was distilled off, and the resulting solid was dissolved in 30 ml of tetrahydrofuran, and phenyllithium diethyl ether solution (1 m
4.5 ml of ol / l) was added and reacted at room temperature for 3 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to give a white solid 1.
6 g was obtained (51% yield). The results of elemental analysis (% by weight) are shown below.

C: 66.3, H: 7.1, N: 5.2,
Zr: 16.3

[0064]

Example 12 (Cyclopentadienyl) bis (2-pyridine-methylate) chlorohafnium {CpHf (OCH ₂ -C ₅ H
Synthesis of ₄ N) ₂ Cl} (Catalyst 12) In a glass reactor having an inner volume of 100 ml, which had been sufficiently replaced with nitrogen, a solution of 2-pyridine-2.0 g of bis (cyclopentadienyl) hafnium dichloride in 2-pyridine was added.
2.3 g of methanol was added, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to give a white solid 1.
1 g was obtained (yield 43%). The results of elemental analysis (% by weight) are shown below.

C: 41.0, H: 3.4, N: 5.5,
Hf: 35.8

[0066]

Example 13 (Pentamethylcyclopentadienyl) bis (2-pyridine-methylate) chlorozirconium {Cp ^* Zr
(OCH ₂ -C ₅ H ₄ N) ₂ Cl} (Catalyst 13) Synthesis of (pentamethylcyclopentadienyl) zirconium dichloride 2.0 g of acetonitrile in a glass reactor having an inner volume of 100 ml, which was sufficiently replaced with nitrogen. 2-in solution
Pyridine-methanol 1.3 g, triethylamine 1.
2 g was added, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to obtain 2.4 g of a yellow solid (yield 8
2%). The results of elemental analysis (% by weight) are shown below.

C: 55.1, H: 5.8, N: 5.6,
Zr: 19.3

[0068]

Example 14 (Indenyl) bis (2-methyl-8-quinolinolate) chlorozirconium {(Ind) Zr (2-Me-
C ₉ H ₅ NO) ₂ Cl} (Catalyst 14) Synthesis (Indenyl) zirconium dichloride 2.0
2.8 g of 2-methyl 8-quinolinol was added to 50 ml of an acetonitrile solution of g, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to give a yellow solid of 1.6.
g was obtained (63% yield). The results of elemental analysis (% by weight) are shown below.

C: 62.3, H: 4.4, N: 4.4,
Zr: 14.0

[0070]

Example 15 (1,2,4-Trimethylcyclopentadienyl) bis (5-chloro-8-quinolinolate) benzylzirconium {(1,2,4-Me ₃ Cp) Zr (5-Cl—C
Synthesis of ₉ H ₅ NO) ₂ (CH ₂ Ph)} (Catalyst 15) Bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride was prepared in a glass reactor with an internal volume of 100 ml that had been sufficiently replaced with nitrogen. 3.8 g of 5-chloro-quinolinol was added to 2.0 g of acetonitrile solution, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The solid obtained by evaporating the filtrate was dissolved in 30 ml of tetrahydrofuran, and a diethyl ether solution of benzyllithium (1 mol / l) was prepared.
3 ml was added and reacted at room temperature for 3 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to obtain 1.7 g of a yellow solid (yield 50
%). The results of elemental analysis (% by weight) are shown below.

C: 61.7, H: 4.5, N: 4.1,
Zr: 14.0

[0072]

Example 16 (Pentamethylcyclopentadienyl) bis (8-quinolinoleate) chlorotitanium {Cp ^* Ti (C ₉ H ₆
Synthesis of (NO) ₂ Cl} (catalyst 16) In a glass reactor having an inner volume of 100 ml which has been sufficiently replaced with nitrogen, 2.0 g of (pentamethylcyclopentadienyl) titanium trichloride in an acetonitrile solution of 50 m
8-quinolinol 2.0 g, triethylamine 1.
4 g was added, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to obtain 1.4 g of a yellow oily substance (yield 3
9%). The results of elemental analysis (% by weight) are shown below.

C: 66.2, H: 5.4, N: 5.6,
Ti: 9.8

[0074]

Example 17 (Trimethylsilyltetramethylcyclopentadienyl) (10-acridinolate) dichlorozirconium {(Me ₃ SiCp *) Zr (C ₁₃ H ₈ NO) Cl ₂ }
Synthesis of (Catalyst 17) In a glass reactor having an inner volume of 100 ml which had been sufficiently replaced with nitrogen, 50 ml of an acetonitrile solution of 2.0 g of (trimethylsilyltetramethylcyclopentadienyl) zirconium trichloride was added to 1.0 ml of 10-acridinol.
g and triethylamine 0.5 g were added, and the mixture was added at room temperature to 12
Stirred for hours. The reaction mixture was dried under reduced pressure, toluene was added, and the mixture was filtered. The filtrate was concentrated and pentane was added to obtain 2.0 g of a yellow solid (yield 72%). The results of elemental analysis (% by weight) are shown below.

C: 54.1, H: 5.5, N: 2.6,
Zr: 16.7 Polymerization reaction

[0076]

[Embodiment 18] 1.6 l of which the inside was vacuum degassed and replaced with nitrogen
5m containing 0.5μmol of catalyst 1 in the autoclave
1 toluene solution and 5 ml of a toluene solution of methylaluminoxane: MMAO (type 4) manufactured by Tosoh Akzo (0.1 mol / l in terms of aluminum) (amount of aluminum: 0.5 mmol) were dehydrated and deoxygenated toluene.
It was put together with 6 l. The internal temperature of the autoclave was maintained at 80 ° C., and ethylene gas was added at 10 kg / cm 2 G. Polymerization was carried out for 1 hour while supplementing ethylene and maintaining the total pressure. 24.3
g of polymer was obtained. The molecular weight Mw is 952000,
The molecular weight distribution Mw / Mn was 2.65.

[0077]

Example 19 Polymerization was carried out in the same manner as in Example 18 using Catalyst 2, yielding 22.1 g of a polymer.
The molecular weight Mw was 960000, and the molecular weight distribution Mw / Mn was 2.86.

[0078]

Example 20 Polymerization was carried out in the same manner as in Example 18 using Catalyst 3, yielding 25.6 g of polymer.
The molecular weight Mw was 862000, and the molecular weight distribution Mw / Mn was 2.10.

[0079]

Example 21: 10 ml containing 1 μmol of catalyst 4 in a glass reactor having an internal volume of 100 ml that had been sufficiently replaced with nitrogen.
Toluene solution and toluene solution of methylaluminoxane MMAO manufactured by Tosoh Akzo Ltd.
mol / l) 10 ml (aluminum amount 1 mmol)
And 1 ml of octene are mixed, and then at 100 ° C for 3
The mixture was heated and stirred for 0 minutes to obtain a toluene preparation liquid.

Into a 1.6 l autoclave whose inside was vacuum degassed and replaced with nitrogen, 10.5 ml of a toluene preparation liquid was placed together with 0.6 l of dehydrated and deoxygenated toluene. Keep the internal temperature of the autoclave at 80 ℃, and add 10kg of ethylene gas.
/ Cm2G was added. Replenish ethylene and keep total pressure 1
Polymerized for hours. 18.0 g of polymer was obtained. The molecular weight Mw is 986000, and the molecular weight distribution Mw / Mn is 2.9.
It was 5.

[0081]

Example 22 Polymerization was carried out in the same manner as in Example 21 using Catalyst 5, yielding 19.6 g of a polymer.
The molecular weight Mw was 1023000, and the molecular weight distribution Mw / Mn was 2.32.

[0082]

[Example 23] The catalyst 6 was polymerized in the same manner as in Example 21 to obtain 20.8 g of a polymer.
The molecular weight Mw was 1025,000, and the molecular weight distribution Mw / Mn was 2.41.

[0083]

[Example 24] The catalyst 7 was polymerized in the same manner as in Example 21 to obtain 21.2 g of a polymer.
The molecular weight Mw was 952000 and the molecular weight distribution Mw / Mn was 2.79.

[0084]

Example 25 10 ml containing 1 μmol of catalyst 8 in a glass reactor having an internal volume of 100 ml which had been sufficiently replaced with nitrogen.
Toluene solution and triisobutylaluminum 1mmo
10 ml of a toluene solution containing 1 l was mixed with a 10 ml toluene solution containing 2 μmol of tris (pentafluorophenyl) borate, and then heated and stirred at 120 ° C. for 10 minutes to obtain a toluene preparation liquid.

15 ml of a toluene preparation liquid was placed in a 1.6 l autoclave whose inside was vacuum degassed and purged with nitrogen together with 0.6 l of dehydrated and deoxygenated toluene. The internal temperature of the autoclave is 80 ℃, ethylene gas is 10kg / cm
2G was added, and ethylene was replenished to polymerize for 1 hour while maintaining the total pressure. 18.8 g of polymer was obtained. The molecular weight Mw was 1023000, and the molecular weight distribution Mw / Mn was 3.65.

[0086]

[Example 26] 1.6 l of which the inside was deaerated in vacuum and replaced with nitrogen
5m containing 0.5 μmol of catalyst 9 in the autoclave
1 toluene solution and a toluene solution of methylaluminoxane MMAO manufactured by Tosoh Akzo Co., Ltd.
1 mol / l) 5 ml (aluminum amount 0.5 mmo
1) was added together with 0.5 l of dehydrated and deoxygenated toluene. Furthermore, 100 ml of 1-hexene was added, the internal temperature of the autoclave was kept at 120 ° C, and 20 kg of ethylene gas was added.
/ Cm2G was added. Replenish ethylene and keep total pressure 1
Polymerized for hours. 31.9 g of polymer was obtained. The molecular weight Mw is 863000, and the molecular weight distribution Mw / Mn is 2.5.
It was 5. The density is 0.908 g / cm3, and the GP
It was confirmed by C-FTIR measurement that 1-hexene was distributed almost uniformly from the low molecular weight region to the high molecular weight region.

[0087]

Example 27 Polymerization was carried out in the same manner as in Example 26 using Catalyst 10, yielding 33.0 g of polymer. Molecular weight Mw is 774000, molecular weight distribution Mw / Mn
Was 2.60 and the density was 0.914 g / cm3.

[0088]

[Example 28] The catalyst 11 was polymerized in the same manner as in Example 26 to obtain 35.0 g of a polymer. Molecular weight Mw is 717,000, molecular weight distribution Mw / Mn
Was 2.66 and the density was 0.916 g / cm3.

[0089]

[Example 29] The catalyst 12 was subjected to polymerization in the same manner as in Example 26 to obtain 30.6 g of a polymer. Molecular weight Mw is 685,000, molecular weight distribution Mw / Mn
Was 3.05 and the density was 0.921 g / cm 3.

[0090]

[Example 30] The catalyst 13 was polymerized in the same manner as in Example 26 to obtain 36.5 g of a polymer. Molecular weight Mw is 743000, molecular weight distribution Mw / Mn
Was 2.33 and the density was 0.910 g / cm3.

[0091]

[Example 31] The catalyst 14 was polymerized in the same manner as in Example 26 to obtain 32.6 g of a polymer. Molecular weight Mw is 721,000, molecular weight distribution Mw / Mn
Was 2.80 and the density was 0.916 g / cm 3.

[0092]

[Example 32] The catalyst 15 was polymerized in the same manner as in Example 26 to obtain 35.2 g of a polymer. Molecular weight Mw is 666000, molecular weight distribution Mw / Mn
Was 2.37 and the density was 0.914 g / cm3.

[0093]

[Example 33] The catalyst 16 was polymerized in the same manner as in Example 26 to obtain 30.4 g of a polymer. Molecular weight Mw is 737,000, molecular weight distribution Mw / Mn
Was 3.46 and the density was 0.911 g / cm3.

[0094]

Example 34 10 m containing 1 μmol of catalyst 17 in a glass reactor having an internal volume of 100 ml which had been sufficiently replaced with nitrogen.
l Toluene solution and triisobutylaluminum 1mm
10 ml of a toluene solution containing ol and a 10 ml toluene solution containing 2 μmol of triphenylcarbonium tetrakis (pentafluorophenyl) borate are mixed,
Then, the mixture was heated and stirred at 30 ° C. for 10 minutes to obtain a toluene preparation liquid.

15 ml of a toluene preparation liquid was placed in a 1.6 l autoclave whose interior was deaerated in vacuum and replaced with nitrogen, together with 0.5 l of dehydrated and deoxygenated toluene. 1-
Add 100 ml of hexene and adjust the internal temperature of the autoclave to 8
At 0 ° C., 10 kg / cm 2 G of ethylene gas was added, ethylene was supplied, and polymerization was carried out for 1 hour while maintaining the total pressure. 33.1
g of polymer was obtained. The molecular weight Mw is 755,000,
Molecular weight distribution Mw / Mn is 2.91, density is 0.916 g.
It was / cm3.

[0096]

[Comparative Example 1] CpZr synthesized according JP _{5-170820 (CH 3 COCH 2 COCH 3} ) 2 Cl
Was used to carry out a polymerization reaction in the same manner as in Example 18. The obtained polymer amount was 5.5 g, and the molecular weight Mw was 34.
The molecular weight distribution was 4000, the Mw / Mn was 2.35, and the density was 0.925 g / cm 3.

[0097]

[Comparative Example 2] Literature Journal of Chemical Society,
Chemical Communications (J.Chem. Soc., Chem. C
ommun., 18, 1415-1417 (1993)).
* Zr using _{((NSiMe 3) 2 CPh)} (CH 2 Ph) 2, was performed in the same manner as in the polymerization reaction as in Example 18. The amount of polymer obtained was 3.4 g, and the molecular weight Mw was 670.
00, molecular weight distribution Mw / Mn is 4.35, density is 0.9
It was 31 g / cm3.

From the comparison between Examples and Comparative Examples 1 and 2, it is clear that when the transition metal compound of the present invention is used as the catalyst component, the catalytic activity is significantly high.

[0099]

EFFECT OF THE INVENTION The olefin polymerization catalyst of the present invention has excellent polymerization activity, and by using this catalyst to carry out a polymerization reaction, a polymer having a narrow molecular weight distribution and a uniform copolymer composition distribution is produced. can do. The resulting polymer exhibits excellent physical properties in terms of impact strength, stress cracking resistance, transparency, low temperature heat sealability, blocking resistance, low stickiness, low extract and the like.

[Brief description of drawings]

FIG. 1 is a flow chart showing a catalyst adjusting step in the present invention.

Claims (6)

[Claims] 1. An olefin polymerization catalyst comprising a transition metal compound represented by the following general formula [1]. CpML ¹ _n Y _3-n ... [1] (In the formula [1], Cp is a group having a cyclopentadienyl skeleton, M is Ti, Zr or Hf. L ¹ is the following general formula. It is represented by the formula [2]. In the formula [2], R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, a halogen atom, an optionally substituted hydrocarbyl group, an alkoxy group or a hydrocarbylsilyl group. . Or, when two adjacent carbon atoms among the carbon atoms forming the skeleton have a hydrocarbyl group which may have a substituent, by bonding to each other 4,
It is a group which may form a 5- or 6-membered ring. X ¹ is O,
S, Se or Te. Y is a halogen atom, an optionally substituted hydrocarbyl group, an alkoxy group,
It is a thioalkoxy group, an aryloxy group, a thioaryloxy group, an amino group or a phosphino group. n is 1 or 2. ) 2. A method for polymerizing an olefin by using the transition metal compound according to claim 1 as a catalyst. 3. An olefin polymerization catalyst comprising the transition metal compound according to claim 1 and an organoaluminum oxy compound. 4. A method for polymerizing an olefin using a catalyst comprising the transition metal compound according to claim 1 and an organoaluminum oxy compound. 5. An olefin polymerization catalyst comprising the transition metal compound according to claim 1 and a cation generator. 6. A method for polymerizing an olefin using a catalyst comprising the transition metal compound according to claim 1 and a cation generator.